西红花药材的化学成分研究
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摘要
采用硅胶柱色谱、硅胶制备薄层、凝胶柱色谱以及半制备高效液相色谱等技术对西红花药材中的化合物进行分离纯化,得到8个化合物。采用一维、二维核磁共振谱、高分辨质谱和红外光谱等技术对化合物进行鉴定。确定得到的8个化合物分别为3,5,5-三甲基-4-羟甲基-2,3-环氧-1-环己酮(1)、(2E,4E)-2-methyl-6-oxo-hepta-2,4-dienoic acid(2)、2,4,4-trimethyl-3-formyl-6-hydroxy-2,5-cyclohexadien-1-one(3)、crocusatin B(4)、(S)-4-羟基异佛尔酮(5)、crocusatin C(6)、crocusatin A(7)和豆甾醇(8)。其中,化合物1为新发现天然产物,化合物2为首次从鸢尾科植物中分离得到,化合物8为首次从西红花药材中分离得到。
Eight chemical constituents of saffron(Crocus sativus L.) were isolated and purified by silica gel column chromatography, silica gel thin layer, Sephadex LH-20 gel column chromatography and semi-preparative high performance liquid chromatography. Identification was carried out by one-dimensional, two-dimensional nuclear magnetic resonance spectroscopies, high-resolution mass spectrometries and infrared spectroscopies. The eight compounds were determined: 3,5,5-trimethyl-4-hydroxymethyl-2, 3-epoxy-1-cyclohexanone(1),(2 E, 4 E)-2-methyl-6-oxo-hepta-2, 4-dienoiacid(2), 2, 4, 4-trimethyl-3-formyl-6-hydroxy-2, 5-cyclohexadien-1-one(3), crocusatin B(4),(S)-4-hydroxy-isophorone(5), crocusatin C(6), crocusatin A(7), and stigmasterol(8). Among them, Compound 1 is a new natural product, Compound 2 is isolated from the Iridaceae for the first time,and Compound 8 is isolated from saffron for the first time.
Eight chemical constituents of saffron(Crocus sativus L.) were isolated and purified by silica gel column chromatography, silica gel thin layer, Sephadex LH-20 gel column chromatography and semi-preparative high performance liquid chromatography. Identification was carried out by one-dimensional, two-dimensional nuclear magnetic resonance spectroscopies, high-resolution mass spectrometries and infrared spectroscopies. The eight compounds were determined: 3,5,5-trimethyl-4-hydroxymethyl-2, 3-epoxy-1-cyclohexanone(1),(2 E, 4 E)-2-methyl-6-oxo-hepta-2, 4-dienoiacid(2), 2, 4, 4-trimethyl-3-formyl-6-hydroxy-2, 5-cyclohexadien-1-one(3), crocusatin B(4),(S)-4-hydroxy-isophorone(5), crocusatin C(6), crocusatin A(7), and stigmasterol(8). Among them, Compound 1 is a new natural product, Compound 2 is isolated from the Iridaceae for the first time,and Compound 8 is isolated from saffron for the first time.
引文
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[9] HENNIG M,PUèNTENER K,SCALONE M. Synthesis of(R)-and(S)-4-hydroxyisophorone by ruthenium-catalyzed asymmetric transfer hydrogenation of ketoisophorone[J]. Tetrahedron:Asymmetry,2000,11(9):1849-1858.DOI:10.1016/S0957-4166(00)00141-5.
[10]徐嵬,陶海燕,杨秀伟.西红花挥发油化学成分的GC-MS分析[J].中国现代中药,2008,10(5):15-17. DOI:10.13313/j.issn.1673-4890.2008.05.007.XU W,TAO H Y,YANG X W. GC-MS analysis of essential oil from the stigma of Crocus sativus L.[J]. Modern Chinese Medicine,2008,10(5):15-17. DOI:10.13313/j.issn.1673-4890.2008.05.007(Ch).
[2]王平,童应鹏,陶露霞,等.西红花化学成分和药理活性的研究进展[J].中草药,2014,45(20):3015-3023. DOI:10.7501/j.issn.0253-2670.2014.20.026.WANG P,TONG Y P,TAO L X,et al. Research progress on chemical constituents of Crocus sativus and their pharmacological activities[J]. Chinese Traditional and Herbal Drugs,2014,45(20):3015-3023. DOI:10.7501/j.issn.0253-2670.2014.20.026(Ch).
[3] CHRISTODOULOU E,KADOGLOU N P,KOSTOMITSOPOULOS N,et al. Saffron:A natural product with potential pharmaceutical applications[J]. Journal of Pharmacy and Pharmacology, 2015,67(12):1634-1649. DOI:10.1111/jphp.12456.
[4] LI C Y,WU T S. Constituents of the pollen of Crocus sativus L. and their tyrosinase inhibitory activity[J]. Chemical&Pharmaceutical Bulletin,2002,50(10):1305-1309. DOI:10.1002/chin.200313168.
[5] STRAUBINGER M,BAU B,ECKSTEIN S,et al.Identification of novel glycosidic aroma precursors in saffron(Crocus sativus L.)[J]. Journal of Agricultural and Food Chemistry,1998,46:3238-3243. DOI:10.1021/jf980119f.
[6] GAO H Y,WANG H Y,LI G Y,et al. Constituents from Zhuyeqing Liquor and their inhibitory effects on nitric oxide production[J]. Phytochemistry Letters,2014,7(1):150-155. DOI:10.1016/j.phytol.2013.11.011.
[7]宋月林,姜勇,毕丹,等.卵叶远志地上部分正丁醇萃取物的化学成分研究[J].中国中药杂志,2012,37(4):471-474. DOI:10.4268/cjcmm20120412.SONG Y L,JIANG Y,BI D,et al. Chemical constituents from n-butanol extract of aerial part of Polygala sibirica[J].China Journal of Chinese Materia Medica,2012,37(4):471-474. DOI:10.4268/cjcmm20120412(Ch).
[8] ZARGHAMI N S,HEINZ D E. Monoterpene aldehydes and isophorone-related compounds of saffron[J]. Phytochemistry,1971,10(11):2755-2761. DOI:10.1016/S0031-9422(00)97275-3.
[9] HENNIG M,PUèNTENER K,SCALONE M. Synthesis of(R)-and(S)-4-hydroxyisophorone by ruthenium-catalyzed asymmetric transfer hydrogenation of ketoisophorone[J]. Tetrahedron:Asymmetry,2000,11(9):1849-1858.DOI:10.1016/S0957-4166(00)00141-5.
[10]徐嵬,陶海燕,杨秀伟.西红花挥发油化学成分的GC-MS分析[J].中国现代中药,2008,10(5):15-17. DOI:10.13313/j.issn.1673-4890.2008.05.007.XU W,TAO H Y,YANG X W. GC-MS analysis of essential oil from the stigma of Crocus sativus L.[J]. Modern Chinese Medicine,2008,10(5):15-17. DOI:10.13313/j.issn.1673-4890.2008.05.007(Ch).